Separation of statistical poly[(N-vinyl pyrrolidone)-co-(vinyl acetate)]s by reversed-phase gradient liquid chromatography

Although size exclusion chromatography (SEC) has been used successfully to determine the molecular weight distribution (MWD) of statistical poly[(N-vinyl pyrrolidone)-co-(vinyl acetate)]s [PVPVAs], SEC cannot separate the copolymers according to their chemical composition. In this article, the separation of commercial PVPVAs with varying chemical compositions is reported, by aqueous reversed-phase gradient liquid chromatography (RPLC) using polystyrene-divinylbenzene-based wide pore columns. RPLC–SEC cross-fractionation indicates the presence of molar mass dependant effects during RPLC separation due to broad MWD for the copolymer studied; therefore the width of the RPLC peak could not be associated entirely with chemical composition distribution of the copolymer. Coupling of RPLC with online FTIR spectroscopy reveals the increase of VA content with increasing THF gradient, an indication of interaction mechanism between VA repeating units and the stationary phase for water soluble PVPVAs. Separation of water insoluble PVPVAs and PVAs by the RPLC are possibly based on both interaction and precipitation/redissolution mechanisms.